To investigate the effects of salt concentration and freeze-thaw (FT) on the first hydration shell of Zn2+ ions in Zn(NO_3)_2 aqueous solutions, extended X-ray absorption fine structure (EXAFS) spectroscopy was used t...To investigate the effects of salt concentration and freeze-thaw (FT) on the first hydration shell of Zn2+ ions in Zn(NO_3)_2 aqueous solutions, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to examine Zn K-edge EXAFS spectra of Zn(NO_3)_2 aqueous solutions with various concentrations before and after FT treatment. The influences of salt concentration and freeze-thaw on the structural parameters of the first hydration shell of Zn2+ ions, including hydration number, Zn-O distance and thermal disorder, were analyzed. The results show that Zn2+ ions have 3.2―6.8 nearest oxygen neighbors with the Zn-O distance being 0.202―0.207 nm. In highly concen-trated solutions, Zn2+ ions are hydrated with four water molecules in a tetrahedral form. The dilution of Zn(NO_3)_2 aqueous solutions increases the number of water molecules in the first hydration shell of Zn2+ ions to six with their octahedral arrangement. Both the hydration number in the first hydration shell of Zn2+ ions and the degree of thermal disorder increase when the FT treatment is operated in Zn(NO_3)_2 aqueous solutions.展开更多
The reaction of triplet fusion,also named triplet-triplet annihilation,has attracted a lot of research interests because of its wide applications in photocatalytic,solar cells,and bioimaging.As for the singlet oxygen ...The reaction of triplet fusion,also named triplet-triplet annihilation,has attracted a lot of research interests because of its wide applications in photocatalytic,solar cells,and bioimaging.As for the singlet oxygen photosensitization,the reactive singlet oxygen species are generated through the energy transfers from photosensitizer(PS)to ground triplet oxygen molecule.In this work,we computed the electronic coupling for singlet oxygen photosensitization using the nonadiabatic coupling from the quantum chemical calculation.Then we utilized the molecular orbital(MO)overlaps to approximate it,where the MOs were computed from isolated single molecules.As demonstrated with quantitative results,this approach well describes the distribution of the coupling strength as the function of the intermolecular distance between the sensitizer and O_(2),providing us a simple but effective way to predict the coupling of triplet fusion reactions.展开更多
基金Supported by National Natural Science Foundation of China(No. 20776096)National Synchrotron Radiation Laboratory, China(No. 20081005G)
文摘To investigate the effects of salt concentration and freeze-thaw (FT) on the first hydration shell of Zn2+ ions in Zn(NO_3)_2 aqueous solutions, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to examine Zn K-edge EXAFS spectra of Zn(NO_3)_2 aqueous solutions with various concentrations before and after FT treatment. The influences of salt concentration and freeze-thaw on the structural parameters of the first hydration shell of Zn2+ ions, including hydration number, Zn-O distance and thermal disorder, were analyzed. The results show that Zn2+ ions have 3.2―6.8 nearest oxygen neighbors with the Zn-O distance being 0.202―0.207 nm. In highly concen-trated solutions, Zn2+ ions are hydrated with four water molecules in a tetrahedral form. The dilution of Zn(NO_3)_2 aqueous solutions increases the number of water molecules in the first hydration shell of Zn2+ ions to six with their octahedral arrangement. Both the hydration number in the first hydration shell of Zn2+ ions and the degree of thermal disorder increase when the FT treatment is operated in Zn(NO_3)_2 aqueous solutions.
基金the supports from the Chinese Academy of Sciences(CAS)Institute of Chemistry,CAS+3 种基金the supports from the National Natural Science Foundation of China(No.21933011)the Beijing Municipal Science&Technology Commission(No.Z191100007219009)the K.C.Wong Education Foundationthe support from the National Natural Science Foundation of China(No.21773073)。
文摘The reaction of triplet fusion,also named triplet-triplet annihilation,has attracted a lot of research interests because of its wide applications in photocatalytic,solar cells,and bioimaging.As for the singlet oxygen photosensitization,the reactive singlet oxygen species are generated through the energy transfers from photosensitizer(PS)to ground triplet oxygen molecule.In this work,we computed the electronic coupling for singlet oxygen photosensitization using the nonadiabatic coupling from the quantum chemical calculation.Then we utilized the molecular orbital(MO)overlaps to approximate it,where the MOs were computed from isolated single molecules.As demonstrated with quantitative results,this approach well describes the distribution of the coupling strength as the function of the intermolecular distance between the sensitizer and O_(2),providing us a simple but effective way to predict the coupling of triplet fusion reactions.
